Novel process and products produced by said process

ABSTRACT

A process for the preparation of mixtures of isomers of octahydro-tetramethyl acetonaphthones comprising reacting myrcene with 3-methyl-3-pentene-2-one to form a substituted acyl cyclohexene Diels-Alder adduct and then cyclizing said DielsAlder adduct with an acid cyclizing agent. The products produced thereby, in particular, the isomer having the structure:   (WHEREIN THE DASHED LINES REPRESENT METHYL GROUPS &#39;&#39;&#39;&#39;CIS&#39;&#39;&#39;&#39; TO ONE ANOTHER) ARE USEFUL AS AMBER AND FRUITY AMBER FRAGRANCE INGREDIENTS. They are also useful for modifying the fragrance and aroma of smoking article side streams and main streams, imparting sweet, spicey, cedarwood-like aromas to such main streams and side streams.

United States Patent Hall et al.

Oct.7, 1975 l NOVEL PROCESS AND PRODUCTS PRODUCED BY SAID PROCESS [75] Inventors: John B. Hall, Rumson; James Milton Sanders, Eatontown, both of NJ,

International Flavors & Fragrances lnc., New York N.Y.

[22] Filed: Jan. 2], 1974 [2|] App]. No: 434,948

Related U.S. Application Data [63] Continuatiomin-purt of Scri No. 33(1 l72 Feb. 27

I973, abandoned [73] Assigneei ()THIER PUBLICATIONS Gould Much and Struct in Org. Chem.." p 537, (1959).

Primary liruminvr Norman P. Morgenstern A/mrmy, Agent, or Firm Arthur L. Liberman, Esq; Harold Haidt, Esq.

[5 7] ABSTRACT A process for the preparation of mixtures of isomers of octahydro-tetramethyl acetonaphthones comprising reacting myrcene with 3mcthyl3-pentene2 -one to form a substituted acyl cyclohexene Diels-Alder adduct and then cyclizing said Diels-Alder adduct with an acid cyclizing agent. The products produced thereby. in particular, the isomer having the structure:

(wherein the dashed lilies represent methyl groups cis" to one another) are useful as amber and fruit amber fragrance ingredients. They are also useful for modifying the fragrance and aroma of smoking article side streams and main streams importing sweet spiccy, cedarwood-like aromas to such main streams and side streams.

5 Claims, 6 Drawing Figures US. Patent 0a. 7,1975 Sheet 1 of6 3,911,018

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F I G .3 MAJOR PEAK FROM EXAMPLE mt INTENSITY I800 I700 I600 I500 I400 US. Patent 0a. 7,1975 Sheet 4 Of6 3,911,018

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Sheet 5 of 6 F 16.5 EXAMPLEIXJI SOLVENT SIGNAL (CHCI IOOO Hz SWEEP WIDTH 0 PPM acrul-ldwv 'IVNSIS SEQ O Oct. 7,1975 Sheet 6 of 6 3,911,018

IP93 mmw m I 000 US. Patent NOVEL PROCESS AND PRODUCTS PRODUCED BY SAID PROCESS This application is a continuation-in-part of application Ser. No. for US. Pat. 336,l72 filed on Feb. 27, 1973, now abandoned.

BACKGROUND OF THE INVENTION Materials which can provide amber fragrance notes are known in the art of perfumery. Many of the natural materials which provide such amber fragrances and contribute desired nuances to perfumery compositions such as ambergris can no longer be obtained or are high in cost or vary in quality from one hatch to another and/or generally subject to the usual variations of natural products.

There is accordingly a continuing effort to find synthetic materials which will replace the essential fragrance notes provided by natural essential oils or compositions thereof having an amber aroma. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odors to the compositions. The search for materials which can provide a more refined amber fragrance has been difficult and relatively costly in the areas of both natural products and synthetic products.

The present invention provides a solution to the aforementioned problem by providing isomer mixtures and a specific isomer and processes for producing same which give rise to unexpectedly intense and persistent natural amber or fruity amber fragrance notes heretofore unknown in the acetonaphthone class of fragrance materials. Indeed, in the perfumers art, there is consid erable need today for substituents having amber or fruity amber fragrance notes which are persistent. Especially desirable are materials which have an amber or fruity amber fragrance note which do not discolor with age. Such amber or fruity amber fragrance materials as stated above have a wide utilization in the preparation of finished perfume compounds. The materials when they are available from natural sources are subject to wide variations in quality, are expensive and are limited or often in critically short supply.

The isomer mixtures and specific isomer of our invention have also been found to modify the smoke side stream and main stream of smoking articles by imparting a sweet, spicey. cedarwood-like aroma to such side streams and main streams. Materials having such properties have been widely sought after in the past but not such materials which are easily available and have relatively low cost have heretofore been discovered. The prior art contains several disclosures of fragrance uses of compounds having structures similar to the compounds contained in the isomer mixtures of our invention and to the specific isomer of our invention.

British Pat. No. 896,039 entitled Method of Produc ing Derivatives of the l l Dimethyloctahydronaphthalene Series discloses the generic process:

-Continucd wherein R R;,, and R are disclosed to be same or dif ferent hydrogen atoms or alkyl and R is disclosed to be hydroxy, alkyl or alkoxy. The British patent discloses this process to be useful for producing products resembling the well known class of violet perfumes. indeed, Example 5 of the British patent alleges that the compound 1 l ,6,6-Tctramethyl-7-ketomethyLOctalin produced by (l) reacting myrcene and mesityl oxide thermally followed by (2) subsequent cyclization, has a pleasant woody ambergris smell. However, a repetition of the teachings of this British patent gives rise to the following results:

STRUCTURE OF COMPOUND CHO NAME:

I, 2', 3', 4, 5', 6', 7', 8'-octahydro-8', 8'(and 5'. 5' )dimethyl-2'-naphthaldchyde PERFUME PROPERTIES:

Green, fruity STRUCTURE OF COMPOUND:

CHO

NAME:

I, 2', 3', 4', 5', 6', 7, 8-octahydro-2, 8', 8(and 2', 5', 5' )-trimethyl-2', napthaldehyde Perfume Properties;

Green floral, fruity STRUCTURE OF COMPOUND:

Clio

3 4 NAME: Perfume Properties: Fruity. woody. pineapple-like l', 2'. 3'. 4" 5', 6', 7', X'mctahydro-fl'. 8, t4'( and 3', and iummumkc 5', 5 )-trimethyl-Z'-naphthaldchydc S'lRLI'lURl: OF COMPOUND Perfume Propertiesi 5 O (ireen. huttery. woody STRUCTURE OF COMPOUND NAM 1 1'. 2'. 5'. 4. 5, 6. 7'. 8'-octahydro-3. 5', 5'-(and K 3, 8'. 8'] trimethylfl acetonaphthone Perfume Properties; l.o\v keyed woody. fruity.

In addition to the ahoye-mentioned British patent, the above stated sequence oi:

AME I. Diels-Alder Reaction to torm Diels-Alder adducts 1', I. 3', 4'. 5. h, 7', N-octahydro 5'.5(and 8', 8' followed by dimethyl-Z'-acetonaphthone Z. Cyclization ofthe Diels-Alder adducts is disclosed in detail by Ohloff Ann. 606.100 1 1957).

The prior art is replete \Kllll disclosures of Diels- STRUCTURE OF COMPOUND: Alder reactions wherein Lewis acids are used as catalysts, as follows:

I. H. (J. Oddy. J.Amer,(hem.Soc.. 452156 (1923),

0 CH3 aluminum chloride catalyzed Diels-Adler reaction of anthracene and maleic anhydride.

*3 2. A, N. Johnson. as, 2.724.730 (1955); CA. 3 51.740911 11957), H AlCL, catalyzed reaction of hexachlorticyclopentadiene with cyclopentene and hexachloroeyclopew Perfume Properties: lononelil\'e tene. 3, P. Yates and P. Eaton..l..-lnu'r.(71011.5()(2. 82.4436 NAME. (1960 l. l, 2', 3', 4, S, 6 7" sl mh dr g, 3', 8" g'u d 35 AlChcataly/ed reaction ofanthracene and maleic an- 3'3', 5. 5) -tetramethyl-2'-aeetonaphthone hydride.

Perfume Properties: Yeasty, Valerian-lik 4. (J. l. Fray and R. Robinson, J..4m('r.('/rvm. Soc,

83,249 (1961); US. 3.067.244 (I962). STRUCI URE 0F COMPOUND: Lewis acid cataly/ed Diels Alder reaction of hutadiene. cyclopentadlene. or anthracene with various dienophiles (e3 acrolein. methacrolein. acrylic 0 acid. methyl vinyl ketone). Only dienophiles hav ing a terminal vinyl group are claimed. CH3 4s H, M. VValhrosky. 1.1.. Barash and T, C. Davis. J.()rg, CH3 ('l'u'ur, 26.4778 1961 'letrahhedron. l9,2333

( 1963 AlCl catalyzed reaction of hutadiene and (-)-dimenthyl fumarate. I I I I NAME. S0 6. I. A. Favorskaya and E. M. Au inen. Zh. ()hS/lC/I, 2 3 t 4 5 6', 7', 8"octahydm-2', 8', 8'(ktl1( l 2', Kin-H 3 27 5 33 CA 59J519] 5, lrimuhylalflccmlmphthnnc BF: catalyzed reaction of isoprene or ZB-dimethyl- Perfume Properties: Fruity. woody, pineapple-like. huwdicnwlj with mclhyl vinyl kcmnc lhcxcw S'fRUCI-URE COMPOUND: 4-one. l-propionylcyclopentene. and l-propionylcyclohexene. 7. E. F. Lutz and G. M. Bailey. J.

Amer. ('ln'm. Sue, 86.3899 (1964). Comparison of isomer ratio of thermal and SnCl4 3 catalyzed reaction 11 isoprene with acrolem or methyl vinyl ketone.

- no 8. T. lnukai and M. Kasai. J. Org. ht'HL. 30.3567 (1965].

(h) '1. lnukai and T, Kojirna. J.()i e.(licm., 3l.l 121 y I I966), NAMI Lewis acid catalyzed reaction of isoprene with vari 1. 2. 3'. 4'. 5'. (1. 7, 8'-octahydro-3 5', Stand 3'. ous acrylic acid derivatives.

8', 8' )-trinicth l-Z'*propioiiaphthone 9, Br. 1.076.304 1965]; CA. 68.49177 f( 1968).

AlCL, catalyzed reaction of methyl acrylate, methyl methylacrylate, or acrylonitrile with isoprene, piperylcne, chloroprene. cyelopentadiene, or 1,3- butadicne. (cf. US. 3,390,169).

10. G. P. Kugatova-Shemyakina, L. l. Rozhkova. V. N. Gramenitskaya and V. M. Andreev, J. Org. Chem. USSR, 6.2459 (1970).

Catalysis of the reaction of acrolein or crotonaldehyde with isoprene or piperylene.

l l. S. R. Wallis, J. Amer. Chem. Soc, 92.3218 (1970). AlCL, catalyzed Diels-Alder reaction of butadiene with Z-phcnyl-2-cyclohexenone.

ln addition, Lewis acid catalyzed Dicls-Alder reactions wherein the dienophile is a, B-disubstituted with alkyl groups are disclosed in our copending US. Pat. application Ser. No. 260,537 filed on June 7, 1972.

Further, cyclization reactions of Diels-Adler adducts of myrcene and a dienophile are set forth in US. Pat. No. 3.076.022. This patent discloses interalia, prepara' tion of the thermal Diels-Alder adduct of myrcene and methyl isopropenyl ketone and subsequent acid cyclization to a product said to possess an intense ambergris-like note". Repetition of the process disclosed gave rise to a product possessing fruity, woody, pineapple notes rather than an ambergris-like note.

Ohloff Chemistry of Odorifcrous and Flavoring Substances] pp. ]85240 (at page 192) Forotschritte und der Chemischen Forschung Vol. 12, Part 2, 1969, discloses a compound'having the structure:

Ohloff indicates that materials of this nature have resiny odors like olibanum, with amber type undertones.

This invention relates to the preparation of synthetic amber-like fragrance ingredients for perfumes and cosmetics and for fragrancing the side streams and main streams of smoking articles containing tobacco. More particularly, the invention has to do with a process for the preparation of amber-like fragrance compositions for use in perfumery and in tobacco composed of octahydro-Z', 3', 8', 8'-tetramethyl-(2'or 3' acetonaphthones in which a majority of said acetonaphthones contains the double bond in the 9'-10' position.

This invention also covers a novel isomer of octahydrotetramethyl acetonaphthone having the structure:

wherein the dashed lines represent methyl groups cis to one another. The invention also covers processes for producing isomer mixtures of octahydro-Z', 3', 8', 8'-

tetamethyl-(l' or 3')-acetonaphthone having the generic structure,

wherein one of the wavy lines is a carbon-carbon double bond and the other of the wavy lines represent carbon-carbon single bonds. The mixtures produced by the processes of our invention contain from mole percent up to 99 mole percent of compounds having the generic structure:

Such a generic structue includes individually compounds having an acetyl group at the 2' position. compounds having an acetyl group at the 3'position and mixtures of such compounds. The generic structures set forth above are also intended to include geometric isomers wherein the acetyl group is eis to the methyl group on the carbon atom adjacent to that bonded to the acetyl moiety and where the acetyl group is "trans to the methyl group on the carbon atom adjacent to that bonded to the acetyl moiety. The processes of our invention give rise to isomer mixtures containing the above-named isomers as well as the isomer having the structure:

Briefly, the novel mixtures of our invention are produced by means of a two step reaction:

I. Reacting myrcene with 3methyI-B-penten-Z-one either:

a. in the presence of a Lewis acid at temperatures in the range of from 0 up to 50C thereby producing a mixture of geometric isomers which are Diels-Alder adducts which are alkenyl acetyl dimethyl substituted cyclohexenes represented by the structure:

or: b. reacting myrcene with 3-methyl-3-penten-Z-one without using a catalyst at temperatures in the range of C up to C forming a mixture of isomers (including geometric isomers) of alkenyl acetyl dimethyl substituted cyclohexenes having the generic structure:

I. Cycliling the resulting substituted cyclohcxenes (DieIsAlder adducts) by means of heating same in the presence of phosphoric acid or dilute sulfuric acid (Stkbtl) or boron trifluoridc or complexes thereof. e.g.. boron tritluroide etherate.

The novel isomer mixtures produced thusly can be further separated by standard physical separation techniques (e.g., chromatographic techniques as set forth in Example XIV) or standard chemical techniques (eg. oximation as set forth in Example Xl) or they can themselves be incorporated into tobacco or tabacco flavors or into a wide variety of finished perfume compounds. it has been found that the novel materials of this invention have persistent fragrances more fully described below which adapts them for incorporation into perfume compounds where a distinct amber or fruity amber fragrance note is required. or into tobacco or tobacco flavors where it is desired to modify aromas of the main stream and side stream of a smoking article on smoking by imparting to the aroma of such main stream and side stream. sweet. spicey. cedarwood-like notes.

In the first of the two reactions of the process of our invention myrcene and 3-methyl3-penten-Z-one are the reactants. Myrcene is generally available at purities of 70'; and upwards and it can be used in this form. It is generally preferred in the practice of this invention to use commercial myrcene [approximately 77% parity) although. obviously. purified myrcene may be used. Such a purification is readily accomplished by fractional distillation The initial reaction may be a thermal Diels-Alder reaction without the use ofa Lewis acid catalyst at a temperature in the range of lZt "lt t)"Cv Preferably. but not necessarily. an antioxidam and polymerization inhibitor such the mixture of fi-naphthylamine and pyrogallol may be utilized, as set forth in Example of British Pat, No. 896.039 Upon performing the first step of the process of our invention by carrying out a thermal Diels-Alder reaction without the use of a Lewis-acid catalyst. the resulting material will be a mixture of approximately 70 weight percent:

and 3t) eight percent:

ltl

with unknown ratios of geometric cis-trans isomers of each. Where the initial DielsAlder reaction is carried out using a Lewis acid catalyst. primarily geometric isomers having one basic structure are obtained. to

wit:

Suitable Lewis acid catalysts are aluminum chloride, stannic chloride. titanium tetrachloride. boron trifluoride. and boron trifluoridc complexes such as boron trifluoride etherates. The Lewis acid catalyst concentra tion workable in our process is from 0.5 up to I00 mole percent based on 3-methyl-3'penten-Z-one with the preferred range being 3-8 mole percent. When using the Lewis acid catalyst. it is preferred that a solvent be used and suitable solvents are toluene. benzene and inert chlorinated hydrocarbon solvents such as chloroform and methylene chloride since they do not take part in the reaction. when using a Lewis acid catalyst. the first reaction is operated at a temperature in the range ofll C up to 50C. preferably C5()C In both the thermal and catalytic Diels-Alder reactions. the mole ratio of myrcene to 3-methyI-B-penten-Lonc may be varied from 1:3 to 3:l or even higher. since the excess reagent may be recovered substantially quantitatively. However. for efficiency and economy as to time. the preferred mole ratio is from 1.1:1 up to l.2:l. The reagents and catalyst may be mixed in any order. however. it is preferred to sequentially add 3methyl-3- pentenJ-one and myrcene to a premix of the catalyst and solvent. the use of solvent in this reaction being preferred also.

The next reaction. following the Diels-Alder reaction. namely cyelization of the acetyl cyclohexene derivative (the Diels-Adlcr adduct), is accomplished by heating the cyclohexene derivative preferably with a mixture of an acid such as phosphoric acid. diluted sulfurie acid. boron trifluroide or boron trifluoride etherate in the presence ofa solvent. The amount of acid cyelization agent may vary from It) up to 100 weight percent based on the weight of the cyclohexene derivative to be cyclired. Preferably. the weight percent of acid should be between and weight percent. preferably. an inert sohent having a boiling point at or about the desired reaction temperature is used in the cyclization reaction The reaction temperature may be anywhere between 25% and the reflux temperature of the reaction mixture. The preferred reaction temperature range is between C and l IS C and accordingly toluene is the preferred solvent since its boiling point at atmospheric pressure is l lU C. 'lhe quantity of solvent used in the cyclization reaction may vary from weight percent up to lUtJ weight percent based on the amount ofcyclohexene derivative being cyclized. lt is preferred to use approximately 50 weight percent of solvent. ln

the cyclization reaction. the order of mixing reagents and solvents is not critical.

The length of time and temperature of the cyelization reaction will determine the percentage of the geometric isomers having the basic structure:

as compared with the geometric isomers having the other possible basic structures, namely:

and

Periods of time of the order of 5-7 hours at temperatures of 7()8()C will yield a mixture wherein isomers having the basic structure(l) will be produced in a quantity of about 8()857z, the remaining isomers having the basic structures (II), (III) and (IV). However, if the cyclization reaction is run for a period of time of approximately l hours, and at 80C greater than 96% of the reaction product has a geometric isomer mixture having the basic structure (I). A temperature of reaction of l lC coupled with a time of reaction of4 hours will also yield a geometric isomer mixture more than 96% of the compounds of which have the basic struc ture (l). A time of reaction of 6 hours coupled with a reaction temperature of l 15C will give rise to a reaction product wherein more than 9992 of the geometric isomers have the basic structure (I ln the event that the first reaction. the Diels-Alder reaction, is carried out using a Lewis acid catalyst. the mixture of isomers produced as a result of carrying out the second cyelization reaction on the resulting Diels Alder reaction product has been found to contain a predominant quantity of an isomer having the structure:

Chromatographic techniques can then be effectively utilized to separate this novel isomer from the cyelization reaction mixture and such a technique is illustrated in Example XIV. infra. This novel isomer has a characteristic intense fruity-amber note. The above isomers are distinguishable from one another by examination of their respective NMR, infrared, and Raman spectra. The fact that the isomers indicated by formulae l and V have a tetrasubstituted double bond, and the isomers indicated by formulae II, III and IV have a double bond which is only trisubstituted and not tetrasubstituted is apparent from a study of FIGS. 1-6.

The two foregoing reactions may be performed in separate reaction vessels or, more preferably, they may be performed in the same reaction vessel whereby the Diels-Alder reaction and subsequent cyclization steps are carried out without isolating the intermediate Diels- Alder adduct, the cyclohexene derivative. Accordingly, when the Diels-Alder reaction is complete, the desired amount of acid is added without any additional solvents, and the reaction mixture is then stirred at the desired temperature until cyclization is complete.

When the cyclization reaction is substantially com plete, the reaction mass is then washed and the organic layer is separated and distilled.

The distilled product may be used as is" or it may be further purified by using gas chromatography techniques and/or oximation (see Example XI) followed by recovery of the purified reaction product from the oxime.

The reaction product mixtures as well as the specific isomer of our invention are clear liquids with intense and persistent unique amber and fruity-amber odors. The isomer mixtures as well as the novel specific isomer of our invention are particularly suited to use as perfume materials in the preparation of perfume compositions and in tobacco and tobacco flavors as modifers of the aromas of the main stream and side stream of the smoke created on smoking smoking articles containing said tobacco. They are very well adapted to perfumery where an amber or fruity-amber aroma is required. They are adapted to modifying tobacco smoke aromas where sweet. spicey, cedarwood aromas are required in the smoke main stream and side stream. The

novel isomer of our invention as well as the oetahydrotetramethyl-acetonaphthone isomer mixtures are par ticularly remarkable for their persistent fruity amber and amber odors. To make an amber or fruity amber type of perfume the materials of this invention can be combined with auxiliary perfume adjuvants" including one or more of many types of odor materials such as hergamot oil vetivert oil, patchouli oil. sandalwood oil. oalt'moss and floral musk, The novel materials of this invention can also be combined with the customary perfume auxiliary adjuvants such as natural oils synthetic oils. aldehydes, ketones, earboxylic acid esters. aryl alcohols. alkanols, lactones, saturated hydrocarbons. unsaturated hydrocarbons, fixatives, solvents. dispersants surface active agents, aerosol propellants, and the like.

The following examples serve to illustrate embodiments of our invention as it is now preferred to practice it. It will he understood that these examples are illustrative and the invention is to he considered restricted thereto only as indicated in the appended claims.

toluene 3-methyl-3-pentenone (2060 g. 959?) is added in 15 minutes to a suspension of aluminum chloride (90 g) in toluene (2 kg). The initial exotherm dies out after ap proximately '7? of the 3methyl-3-pentenone is added. The mass is warmed to 35C. and myrcene (3530 g, 77% was added over a period of 2 hours with external cooling as needed to maintain the reaction mixture at 35 40C. The mixture is stirred at 35 40C for 2 hours 27 g aluminum chloride is added, and the mass is stirred an additional 9 hours at 35 40C.

After standing overnight at room temperature, the mixture is washed at 40C with sodium chloride solution and sodium sulfate solution The washed organic solution is mixed with 100 g triethanolamine, 100 g Primol (U.S. P. white mineral oil available from Exxon Incorporated of Linden, NJ.) and 5 g l0nol (registered trademark of the Shell Chemical Company: butylated hydroxy toluene) and is distilled rapidly at Z*3.5 mm Hg using a short column to give 3999 g of product hp IJo ASU CIZ-AS mm Hgv IR analysis (Peaks) 2962, 2904, 2840, I698 l45() 14301380. 1373, 135l, 1222,1195, 11601138.!098, I090, 1080 cm ('hemleil Shifts 4 Note l l Interpretation 5.1% 5 1H. broad) s 502 5 l IH. smith o ltl 1 112.5(! 5 (9H. mull l H Zilhfiillsmgi O 102 fifill mt'l CH l -l 3 3H. sing l U92 Still-sing) o ll 7! 5 l .H. doul lell o fi C H (in H i \nh E \II nnt'ltuu vimum'tu resonance clumual liilts .tfi. reprint-d in parts per million lkl.l|l\\ to l\ll.ll\lLll\\|\l|-IIIL Mass Spectral Anal \sis: iii/e Z34 (MU. l9l. I23,

13 EXAMPLE n The product of Example 1 (3 kg, 98.7%) is added over a period of 45 minutes to a well-stirred mixture of 1.5 kg of toluene and 1.5 kg of 85% phosphoric acid maintained at 70 80C. The mixture is stirred vigorously at 70 80C for 5.5 hours and then is cooled and mixed with 3 kg of crushed ice. The organic phase is subsequently washed with sodium chloride solution 10% sodium carbonate solution and saturated sodium chloride solution. The washed organic solution is mixed with triethanolamine (100 g), Primol (50 g) and lonol (3 g) and is rapidly distilled under reduced pressure using a short column.

Fractionation of the crude product gives 2604 g of a mixture of geometric isomers (bp l34l35C/2.8 mm

Hg) having an intense amber aroma.

Using GLC analysis, this material shows two major peaks (Varian Aerograph model 200, 10 feet X Ainch, 5% Carbowax K 20 M on chromosorb G, helium flow rate 80 cc per minute, temperature programmed 3S l00200C at l0C/min.), Peak 1 93%. Peak 2 7%. Peaks 1 and 2 are trapped from the above column. The NMR spectra of the two peaks are quite different. The NMR analysis for Peak 1 is set forth in Table l and is as follows:

Table 1 Chemical Shil'ts Interpretation 2.1o5l3H. single!) 0 l.l)(l 5 (3H. singlet) 0.98 8 (6H singlet) and mu 5(3H. liullet. 0

mp1, w

The NMR analysis for Peak 2 is set forth in Table 2 and is as follows:

Table 2 Chemical Shifts Interpretation 5.32 8 lH. broad multiplet) 2.ll 5 (3H. singlet) O A c H 1.08 8 (3H singlet) c H3 0.8) 5 (3H, singlet) 0.76 5 (3H. singlet) H C CH Table lContinued 'hemical Shuts Interpretation ll (6*: H181llllLmultipleU and/or IR analtsts for Peak I 29511 ZUZL 1701 1-155, 14411, 133i 135). 1:35. llift 117R 115% 1121i 1lll3 lll l ltttsililwm Mass spectra] -llllll)\l for Peak 1.

Generic structure of isomers of mixture of Peak 1:

Peak 1 has a slight buttery note with a strong woody amher character Peak 2 is weak, low keyed with a green \egetahle character EXAMPLE 111 A perfume composition is prepared by admixing the following ingredients in the indicated proportions:

lilo

Lintt1 \l Acetate Phen \l lth \l Alcohol Pclitgrani 5A (Ill (ontinued Ingredient Amount ((jrantsl Bergamot Oil Alpha Mclhxl lonone 3'rtihh' tetraniethylI'stcclo naphlhones produced h the process separatlultl (ycli/etl HIL'}L'1U l 1 material produced according to the (anadizln Patent -1115 Issued October 111 197(1 lso Horn ("\clohex tl Alcohol Ben/ 1 Acetate I'n'Heptfl clopentanonc 5 (TOTAL! 353 3 lit The foregoing blend is evaluated and found to have a high degree of richness and persistence in its novel natural amber quality. This base composition can be admixed with aqueous ethanol. chilled and filtered to produce a finished cologne The cologne so prepared has an amber aroma leaning towards a woody amber note. The base composition can also be used to scent soap or other toilet goods such as lotion aerosol. sprays and the like.

EXAMPLE 1V Into a 2 liter reaction vessel equipped with stirrer thermometer and reflux condenser the following ingredients are placed:

Allll grants M \rcenc (77') l 128 grams xrrl't' .1Methyl-lpentenulone I grant l0n0l (Registered trademark ofthe Shell (hemical (0.) lButylated Hydro 'l'oluenel 51) grams l oluenc EXAMPLE V The Diels-Alder product of Example 1V is added over a period of minutes to a well-stirred mixture of grams toluene and 100 grams (\Z'f? sulfuric acid maintained at TU HU C The mixture is stirred vigorously at 711 801 for o hours and is then cooled and mixed with l kilogram of crushed ice. The organic phase is subse quently washed with 10? sodium chloride solution.

l()'7( sodium carbonate solution and saturated sodium chloride solution. The washed organic solution is then mixed with triethanolamine (20 g). Prirnol (5 g) and lonol (1 g) and is rapidly distilled under reduced pressure using a short column. In this way, a product is obtained containing only traces of uncyclized starting material and containing geometric isomers having the basic generic structure:

EXAMPLE VI Diels-Alder adduct mixture prepared according to the process of Example IV 85% phosphoric acid toluene 250 grams 25H grams The reaction mass is heated to reflux at atmospheric pressure l l8C) and maintained at reflux for a period of 3 A; hours after which time the reaction mass was cooled down. The reaction mass is then washed with one liter portion of water; then two 500 cc portions of water; then one 500 cc portion of 5% sodium carbonate and finally one 500 cc portion of saturated sodium chloride. The washed reaction mass is then stripped of solvent thereby giving rise to 445 grams of crude product The crude product is then rushed over and distilled through a fractionation column after adding to it 2 grams of calcium carbonate, 3() grams of Primol and l gram of Ionl at a vapor temperature of l24l26C and 2.1-2.8 mm. Hg. pressure IR, NMR and mass spectral analyses yield the informaton that the resultant product is a mixture of geometric isomers having chemical structures, 70% of which have the generic structure:

and 30% of which have the generic structure:

wherein one of the wavy lines in each of the above structures is a carbon-carbon double bond and the other of the wavy lines in each of the above structures represents a carbon-carbon single bond.

EXAMPLE vu Into a 5 liter reaction flask equipped with stirrer, reflux condenser, addition funnel and thermometer. the following ingredients are placed:

aluminum chloride toluene 53 grams 500 grams 545 grams of 3-methyl3-pentene-2-one is then added through the addition funnel into the 5 liter reaction flask over a period of 5 minutes, the temperature of the mass rising to 41C. Immediately thereafter, 975 grams of 777( myrcene is added, with stirring, to the reaction vessel over a period of l hour while maintaining the temperature of the mass at 405()C. The reaction mass is then maintained at 4()5()C for a period of 4 /2 hours after which period 300 grams of phosphoric acid is added through the addition funnel. The reaction mass is then heated to l()()l 15C and maintained at that temperature for a period of 8 hours. At the end of the reaction, the reaction mass is washed with two 1 kilo portions of 50C water; then one 250 cc portion of 50C I071 sodium carbonate solution; and finally one 500 gram portion of 50C 15% sodium sulfate solution. After separation of the organic phase from the aqueous phase, 2l5 grams of triethanolamine is added to the reaction mass. The 5 liter reaction vessel is then equipped with stirrer, reflux condenser, ther mometer and Bidwell trap and the mass is then heated to reflux 128C) while removing solvent thereby gradually increasing the pot temperature to C. After 8 hours, sampling of the reaction mass and analysis thereof yielded the information that no labile organic halide is present in the reaction mass. The reaction mass is then stripped of solvent, the crude mass weighing [410 grams. The crude product is rushed over and then fractionated after adding 40 grams Primol 1 gram lonol and 10 grams calcium carbonate and purging with nitrogen, at a l l reflux ratio at vapor temperature of l29l3lC and 2.6-2.9 mm. Hg. pressure. Yield 845 grams.

The major peak is separated out by GLC analysis in accordance with the same procedure as is set forth in Example II. The Raman spectrum for the major peak (using a Raman spectrometer manufactured by Spex Incorporated of Plainficld. NJ.) is. in part. set forth in FIG. 3. The Raman spectrum indicates a tetrasuhstituted double bond at I679 cm" and a carbonyl group at l7l 1 cm".

The infrared analysis for the major peak is set forth in FIG. 4.

The NMR analysis for the major peak is set forth in FIG. 1

IR, NMR and Raman spectral analyses yield the information that the resulting product is a mixture of iso mcrs having the generic structure:

EXAMPLE 'lll A perfume composition is prepared exactly as in Example [ll except that the mixture ofisomers of 1,2',3,- 4'5'.h',7'.8-octahydro-2',3',8'.8-tetramethyl-2'- aeetonaphthones produced by the process of Example Vll is applied in lieu of the mixture of Example 11 (prior to GLC separation I.

This blend is evaluated and found to have a high degree of richness and persistence in its novel natural amber quality. This composition can he admixed with aqueous 95" ethanol (ratio: 95 parts ethanol: parts composition] chilled and filtered to produce a finished cologne. The cologne so prepared has an amber aroma leaning towards a woody amber note. The composition can also he used to scent soap or other toilet goods such as lotion, aerosol, sprays and the like.

EXAMPLE IX Autoclave Reaction of Myrcene and 3-Methyl-3-Pentene-Z-One Ihermal Reaction Non-Catalytic) Into a one liter stirred autoclave, the following ingredients are placed:

Myrcene 4 1'7" 1 400 grams -MethxI-R-Pentene- I-One [90" 220 grams l0nol 1 gram Toluene grams structure:

EXAMPLE X Cyclization of Diels-Alder Adduct Mixture of Example lX Phos horic Acid 1 W 1 Toluene 150 grams 275 grams The toluene-phosphoric acid mixture is heated to 100C. Over a period of 15 minutes, the DielsAlder adduct isomer mixture of Example lX is added. The cyelization reaction is carried out over a period of 5 hours at temperatures in the range of l 10C-l 15C. At 50C. the reaction mass is then washed with two 500 gram portions of water. one 500 gram portion of saturated sodium carbonate (to pH of and one 15)? solution of sodium sulfate. The toluene is then stripped off and reaction mass is rushed over at 1-1.5 mm. Hg. pressure and a vapor temperature of ll0l 17C. The rushed over material is then distilled at a vapor temperature of 128 1 32C and a pressure of 2.5 mm. Hg. (reflux ratio 9:1). GLC. NMR. IR and mass spectral analysis yield the information that the resulting product is a mixture of isomers having the generic structure:

EXAMPLE Xl A. Preparation of Oxime In a two liter flask is placed 1000 ml of 957: aqueous ethanol and 61 gms. of hydroxylamine sulfate. The re action mass is stirred while a solution of 30 gms. of sodium hydroxide in 30 gms. of water is added slowly. After an additional 35 minutes of stirring, the reaction mass is filtered to remove the suspended sodium sulfate.

The resulting alcoholic solution of hydroxylamine is charged to a two liter three neck flask and l 15 gms. of material prepared as in Example Vll (prior to GLC separation] is added. The resultant mixture is stirred vigorously at reflux for approximately 8.5 hours. The solution is cooled to room temperature and the resulting crystals are filtered and air dried to give 70 gms of oxime. The oxime is crystalized twice from toluene (23 ml toluene per gram oxime) to get 50 gms. purified ox- B. Regeneration of l',1',3,4',5'.6',7',8'-Octahydro- 2.,3'.8,s l etramethylu'-Acetonaphthone A mixture of 50 guts. of the recrystaliyed oxime produced in Part A herein. 250 gms. of 10? weight/weight sulfuric acid. and 500 gms. of'1' aqueous ethanol is stirred at reflux for 4.5 hours. The mixture is washed with 2500 ml. of sodium hydroxide solution and then with water. Toluene (100 ml) is added to the organic layer and the material is stripped under reduced pressure lO- ml Hg pressure) to remove traces of water. The washed and dried product is then distilled to give 30 gms. of product which is essentially identical to the product of Example XIV by comparison of NMR spectra and GLC elution times. The NMR analysis of this material is set forth in FIG. 6.

This material is evaluated as being a very clean version of the material prepared in accordance with the process of Example VII, significantly better than the material which contains other isomers.

EXAMPLE XII A perfume composition is prepared exactly as in Example lll except that the mixture of isomers of l ',2',3',- 4,5,6,7,8'-octahydro-2,3',8',8'-tetramethyl-2- acetonaphthones produced by the process of Example X is employed in lieu of the mixture of Example ll.

This blend is evaluated and found to have a high degree of richness and persistence in its novel natural amber quality. This composition can be admixed with aqueous ethanol, chilled and filtered to produce a fin ished cologne. The cologne so prepared has a citrus aroma leaning towards an amber note. The composition can also be used to scent soap or other toilet goods such as lotion, aerosol, sprays and the like.

EXAMPLE Xlll The Diels-Alder reaction product of Example IV (250 gms. thereof) is added over a period of 50 minutes to a well stirred mixture of l000 gms. of toluene and 145 gms. of boron trifluoride diethyl ether complex in a 3 liter reaction vessel equipped with stirrer, reflux condenser. thermometer, and addition funnel. The reaction mass is then maintained at 485 lC over a period of 13 hours and is then cooled to less than C with stirring. While being maintained at 25C, 600 gms. of IO aqueous sodium hydroxide is added to the reaction mass. The resulting organic layer is then washed with 10% sodium hydroxide and water. The reaction mass is then stripped of solvent thereby yielding 332 gms. of crude product. The crude product is fractionated at a vapor temperature of l25l 28C and a pressure of 2.2 mm. Hg. after 30 gms. of Primol, 1 gm. of lonol and 5 gms. of calcium carbonate is added thereto. In this way, a product is obtained containing geometric isomers having the basic generic structure:

EXAMPLE XIV The major GLC peak of the product of Example VlI is trapped from a 500 foot X 0.03 inch, SF96 (a nonpolar silicone polymer manufactured by Analabs Inc. of R0, Drawer 5397, Hamden Conn. 06518) column (L at 185C isothermal. This peak is 86.171 of the total material produced (according to GLC on a similar column). The trapped peak is 99.992 one peak when rechromatographed on a 500 foot X 0.03 inch, SF96 column programmed -l C at 4C/min.

The trapped material is submitted for NMR analysis and the results are as follows:

Chemical Shifts interpretation 62.09 3H. sharp singlet o 52.40-l .20, l lH. complex muitiplct 8L0]. 3H. sharp singlet 8090, 6H, broadened singlet C H 3 CH 60.80, douhleL J 7 cps 50.82, doublet. J 7 cps The NMR analysis is set forth in FIG. 5.

O 112. ll

EXAMPLE XV A perfume composition is prepared exactly as in Example lll except that the tetramethyl acetonaphthone isomer having the structure:

produced by the process of Example XI or Example XIV is employed in lieu of the mixture of Example II.

The foregoing blend is evaluated and found to have a high degree of richness and persistence in its novel natural amber quality. This composition can be admixed with aqueous 957: ethanol (ratio: parts ethanol:5 parts composition) chilled and filtered to produce a finished cologne. The cologne so prepared has an amber aroma leaning towards a woody amber note. The composition can also be used to scent soap or other toilet goods such as lotion, aerosol, sprays and the like.

EXAMPLE XVI Preparation of a Soap Composition A total of lllll gins. of soap chips produced from unperfumed sodium based toilet soap made from tallow and coconut oil are mixed with l gm. of the perfume composition set forth in Example XV until a substan tially' homogeneous composition is obtained. The soap composition manifests a characteristic amber aroma.

EXAMPLE XVII Preparation of a Soap Composition A total of I gms. of soap chips produced from unperfumed sodium based toilet soap made from tallow and coconut oil is mixed with l gm of the isomer pro duced using the process of Example XI or Example XIV until a substantially homogeneous composition is obtained. The soap composition manifests a fruity amher character.

EXAMPLE XVIII Preparation of a Detergent Composition A total of I00 gms. ofa detergent powder sold under the trademark RINSO are mixed with 0.15 gms. of a perfume composition containing the mixture obtained in Example XV until a substantially homogeneous com position having an amber fragrance is obtained.

EXAMPLE XIX Preparation of a Cosmetic Base A cosmetic powder is prepared by mixing 100 gms. of talcum powder with (1.25 gms. of the perfume com position of Example XV in a ball mill. A second cosmetic powder is similarly prepared except that the mixture produced in Example XV is replaced with the product produced in Example XI or Example XIV. The cosmetic powder containing the material of Example XV has an amber fragrance. The cosmetic powder produced using the material produced in Example XI or Example XIV has a fruity amber character.

EXAMPLE XX Liquid Detergent Concentrated liquid detergents with fruity amber odor containing (1.2%. 0.57: and LEW of the product produced in accordance with Example XI or Example XIV are prepared by adding the appropriate quantity of the specific isomer so produced to liquid detergent known as P-B'l. The fruity amber aroma of the liquid detergent increases with increasing concentration of the isomer of Example XI or Example XIV.

EXAMPLE XXI Preparation of Cologne and Handkerchief Perfume The composition of Example XV is incorporated in a cologne having a concentration of 2.55% in 85% aqueous ethanol; and into a handkerchief perfume in a concentration of (in 95% ethanol). The use of the composition of Example XV affords a distinct and definite amber aroma to the handkerchief perfume and to the cologne.

EXAMPLE XXII Preparation of Cologne and Handkerchief Perfume The specific isomer produced by the process of Example XI or Example XIV is incorporated into a cologne ha\ing a concentration of 2.57r in ethanol; and into a handkerchief perfume in a concentration of It); (in ethanol The specific isomer having the structure:

produced in Example XI or Example XIV affords a distinct and definite fruity amber aroma to the handkerchief perfume and to the cologne.

EXAMPLE XXIII A tobacco blend is prepared as follows:

The abovementioned tobacco blend is divided into four portions: Portion A; Portion B; Portion C; and Portion D. Portion C and D are each combined separately with the abovemcntioned tobacco flavor formulation. at the rate of(l.27(. Each of Portions A. B, C and D are then manufactured into cigarettes. The cigarettes containing tobacco Portions A and C are left as is. To the cigarettes manufactured from tobacco Portions B and D are added at the rates of 200 and 2000 ppm the mixture of isomers of l',2',3',4',5',6',7',8'-octahydro- 2,3,8',8'tetramethyI-2'-acetonaphthone produced by the process of Example VII. The cigarettes are then evaluated by paired comparison and the results are as follows.

The aroma on smoking of cigarettes produced from tobacco Portions B and D are found to be more sweet aromatic. more woody, more green and more spicey (sandalwood. cedarwood-like) than the aroma of those cigarettes produced from Portions A and C.

In smoke flavor (main stream) the cigarettes produced from Portion D are found to be more aromatic.

more sweet, more green. more bitter, woodier, slightly floral and to have a mouth coating effect.

In smoke flavor (side stream or room aroma) the cigarettes produced from Portion D are found to be more sweet. aromatic. more woody and more spicey. i.e.. having an oriental. balsamic, sandalwood, cedarwoodlike character.

The mixture of isomers of l',2',3',4',5',6',7'.8'- octah vdro2',3,8'.8'-tetramethyl-2'-acetonaphthones produced by the process of Example VII modifies the side stream and main stream smoke aromas by imparting thereto a pleasant, spicey. sandalwood. cedarwoodlike character.

All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

In the accompanying drawings forming part of this application, the figures which represent charts referred to in the above examples are listed as follows:

FIG. I is a chart showing the nuclear magnetic resonance spectrum of peak No. I trapped by gas chromatography techniques from the product produced by the process of Example II or the major peak trapped by gas chromatography techniques from the product of Example VII.

FIG. 2 is a chart showing the nuclear magnetic resonance spectrum of peak No. 2 trapped by gas chromatographic techniques from the material produced by the process of Example II.

FIG. 3 is a portion of the Raman spectrum of the major peak trapped by gas chromatographic techniques from the material produced according to the process of Example VII.

FIG. 4 is an infrared analysis spectrum of the material which is the major peak trapped by gas chromatographic techniques from the material produced according to the process of Example VII.

FIG. 5 is a nuclear magnetic resonance spectrum of the material produced according to the process of Example XIV.

FIG. 6 is the nuclear magnetic resonance spectrum of the product produced according to the process of Example XI.

What is claimed is:

I. The process for producing an amber-like fragrance composition containing a major proportion l',2',3',4'.5',o',7'. 8'-octahydro2',3',R',H'- tetramethyl acetonaphthonc isomers comprising the steps of:

i. Admixing at a temperature of from about 0C up to about 50C myrcene and 3-meth 'l-3-pentene Z-one in the presence of a Lewis acid catalyst thereby forming a acetyl substituted cyclohexene mixture.

'. Cyclizing the resulting acetyl substituted cyclohexenc mixture with a cyclizing agent selected from the group consisting of concentrated phosphoric acid. sulfuric acid. boron trifluoride and complexes of boron trifluoride; and

iii. Obtaining a distillation fraction having a boiling point of l 29-] 3 lC at a pressure of about 2.6 s 2.) mm Hg.

2. The process of claim I wherein the first step and the second step are carried out in the same reaction vessel, without isolating the acetyl substituted cyclohexene isomer mixture.

3. The process of claim 1 wherein the first reaction step is carried out at a temperature in the range of from 35C up to 50C and the second reaction is carried out in the presence of toluene as solvent at a temperature of from C up to l 15C.

4. The product of the process of claim I.

5. A composition consisting essentially of a compound having the structure:

I .ll

other. 

1. THE PROCESS FOR PRODUCING AN AMBER-LIKE FRAGRANCE COMPOSITION CONTAINING A MAJOR PROPORTION OF 1'',2'',3''84'',5'',6'',7'', 8''-OCTAHYDRO-2'',3'',8'',8'',-TETRAMETHYL ACETONAPHTHONE ISOMERS COMPRISING THE STEPS OF: I. ADMIXING AT A TEMPERATURE OF FROM ABOUT 0*C UP TO ABOUT 50*C MYRCENE AND 3-METHYL-3-PENTENE-2-ONE IN THE PRESENCE OF A LEWIS ACID CATALYST THEREBY FORMING A ACETYL SUBSTITUTED CYCLOHEXENE MIXTURE, II. CYCLIZING THE RESULTING ACETYL SUBSTITUTED CYCLOHEXENE MIXTURE WITH A CYCLIZING AGENT SELECTED FROM THE GROUP CONSISTING OF CONCENTRATED PHOSPHORIC ACID, SULFURIC ACID, BORON TRIFLUORIDE AND COMPLEXES OF BORON TRIFLUORIDE, AND III. OBTAINING A DISTILLATION FRACTION HAVING A BOILING POINT OF 129-131*C AT A PRESSURE OF ABOUT 2.6 - 2.9 MM HG.
 2. The process of claim 1 wherein the first step and the second step are carried out in the same reaction vessel, without isolating the acetyl substituted cyclohexene isomer mixture.
 3. The process of claim 1 wherein the first reaction step is carried out at a temperature in the range of from 35*C up to 50*C and the second reaction is carried out in the presence of toluene as solvent at a temperature of from 95*C up to 115*C.
 4. The product of the process of claim
 1. 5. A composition consisting essentially of a compound having the structure: 